PHOTOALIGNING POLYMER MATERIALS

Abstract

The present invention relates to novel photoaligning polymer materials, to their use as orienting layer for liquid crystals, which are used for the production of non-structured and structured optical elements, electro-optical elements, multi-layer systems or in nanoelectronics.

Claims

1. A photoaligning polymer material comprising repeating structural units of formula (I) ##STR00027## wherein M.sup.1, M.sup.1 each independently signify a repeating monomer unit from the group; acrylate, methacrylate, 2-chloroacrylate, 2-phenyl acrylate, acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, N-lower alkyl substituted acrylamide, N-lower alkyl substituted methacrylamide, N-lower alkyl substituted 2-chloroacrylamide, N-lower alkyl substituted 2-phenylacrylamide, vinyl ether, vinyl ester, styrene, diamine, amide, imide, siloxane, amic ester, amic acid; S.sup.1 is a spacer unit, wherein, if m and n are 0 then the spacer unit is S.sup.2 and if at least one m or n is 1, then the spacer unit is S.sup.3; S.sup.1 is a spacer unit, wherein, if m and n are 0 then the spacer unit is S.sup.2 and if at least one m or n is 1, then the spacer unit is S.sup.3; wherein S.sup.2, S.sup.2, S.sup.3, S.sup.3 are unsubstituted or unsubstituted, straight-chain or branched, (CH.sub.2).sub.r, as well as (CH.sub.2).sub.rO, (CH.sub.2).sub.rO(CH.sub.2).sub.s, (CH.sub.2).sub.rO(CH.sub.2).sub.sO, (CH.sub.2).sub.rCO, (CH.sub.2).sub.rCOO, (CH.sub.2).sub.rOCO, (CH.sub.2).sub.rNR.sup.2, (CH.sub.2).sub.rCONR.sup.2, (CH.sub.2).sub.rNR.sup.2CO, (CH.sub.2).sub.rNR.sup.2COO or (CH.sub.2).sub.rNR.sup.2CONR.sup.3, which is optionally mono- or multiply-substituted with C.sub.1-C.sub.24-alkyl, or hydroxy, fluorine, chlorine, cyano, ether, ester, amino, amido; and wherein one or more CH.sub.2 group may be replaced by a linking group, alicyclic or aromatic group; and, in which r and s are each a whole number of 1 to 20, with the proviso that 3r+s24 for S.sup.2; and that 6r+s24, for S.sup.3; and R.sup.2 and R.sup.3 each independently signify hydrogen or lower alkyl; and rings A, A each independently signify phenylene which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy, pyridine-2,5-diyl; pyrimidine-2,5-diyl; 1,3-dioxane-2,5-diyl; cyclohexane-1,4-diyl; piperidine-1,4-diyl; piperazine-1,4-diyl; rings B, B each independently signify phenylene which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy; pyridine-2,5-diyl; pyrimidine-2,5-diyl; 1,4- or 2,6-naphthylene; 1,3-dioxane-2,5-diyl; cyclohexane-1,4-diyl; Y.sup.1, Y.sup.2, Y.sup.1, Y.sup.2 each independently signify a single covalent bond, (CH.sub.2).sub.t, O, CO, COO, OOC, CF.sub.2O, OCF.sub.2, NR.sup.4, CONR.sup.4, R.sup.4NCO, (CH.sub.2).sub.uO, O(CH.sub.2).sub.u, (CH.sub.2).sub.uNR.sup.4 or NR.sup.4(CH.sub.2).sub.u, in which R.sup.4 signifies hydrogen or lower alkyl; t signifies a whole number of 1 to 4; u signifies a whole number of 1 to 3; rings C, C each independently signify phenylene which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy; or pyrimidine-2,5-diyl; pyridine-2,5-diyl; 2,5-thiophenylene; 2,5-furanylene; 1,4- or 2,6-naphthylene; Z, Z each independently signify O or NR.sup.5, in which R.sup.5 signifies hydrogen or lower alkyl, or a second group of formula D or D, in which D is a C.sub.1-C.sub.3 straight-chain or branched alkylene chain which is halogenated at least once or contains one or more siloxane moieties; and D signifies hydrogen or a straight-chain or branched alkylene group with 1 to 20 carbon atoms which is optionally substituted with halogen, a cycloalkyl residue with 3 to 8 ring atoms which is optionally substituted with halogen, alkyl or alkoxy; and and w and w.sup.1 are molar fractions of the comonomers with 0<w1 and 0w.sup.1<1.

2. The photoaligning polymer material according to claim 1, wherein the photoaligning material is a homopolymer.

3. The photoaligning polymer material according to claim 1, wherein the photoaligning material is a copolymer.

4. The photoaligning polymer material according to claim 1, wherein M.sup.1, M.sup.1 are independently from each other a monomer unit selected from the group consisting of acrylate and methacrylate; rings A, A are unsubstituted phenylene or phenylene which is substituted with alkyl or alkoxy; rings B, B are unsubstituted phenylene or phenylene which is substituted with fluorine, alkyl or alkoxy; Y.sup.1, Y1, Y.sup.2, Y.sup.2 each independently is a single covalent bond, COO, OOC; m, n, m, n each independently is 0 or 1; rings C, C are unsubstituted phenylene or phenylene which is substituted with alkyl or alkoxy; S.sup.1, S.sup.1 is a spacer unit, wherein, if m and n are 0 then the spacer unit is S.sup.2 or S.sup.2 and if at least one m or n is 1, then the spacer unit is S.sup.3 or S.sup.3; wherein S.sup.2 or S.sup.2 is C.sub.4-C.sub.24alkylene, preferably alkyleneoxy, or alkyleneoxycarbonyl, especially propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, octyleneoxy, nonyleneoxy, deyleneoxy, or propylenoxycarbonyl, butylenoxycarbonyl, pentylenoxycarbonyl, hexyl enoxycarbonyl, heptylenoxycarbonyl, octylenoxycarbonyl, nonylenoxycarbonyl, deylenoxycarbonyl; and wherein S.sup.3 or S.sup.3 is C.sub.8-C.sub.24alkylene, and wherein alkylene is unsubstituted or substituted, straight-chain or branched alkylene, in which one or more CH.sub.2 groups may be replaced by at least one linking group, alicyclic or/and aromatic group, Z, Z.sup.1 are O, D is a C.sub.1-C.sub.3 straight-chain or branched alkylene chain which is halogenated at least once or contains one or more siloxane moieties; and D signifies hydrogen or a straight-chain or branched alkylene group with 1 to 20 carbon atoms which is optionally substituted with halogen, a cycloalkyl residue with 3 to 8 ring atoms which is optionally substituted with halogen, alkyl or alkoxy.

5. The photoaligning polymer material according to claim 1, wherein rings C, C each independently signify phenylene which is unsubstituted or optionally substituted with fluorine, chlorine, cyano, alkyl or methoxy; or pyrimidine-2,5-diyl; pyridine-2,5-diyl; 2,5-thiophenylene; 2,5-furanylene; 1,4- or 2,6-naphthylene.

6. The photoaligning polymer material according to claim 1, wherein S.sup.1 is a spacer unit, wherein, if m and n are 0 then the spacer unit is S.sup.2 and if at least one m or n is 1, then the spacer unit is S.sup.3; S.sup.1 is a spacer unit, wherein, if m and n are 0 then the spacer unit is S.sup.2 and if at least one m or n is 1, then the spacer unit is S.sup.3; wherein S.sup.2, S.sup.2, S.sup.3, S.sup.3 are substituted or unsubstituted, straight-chain or branched, (CH2)r-, as well as (CH2)r-O, (CH2)r-O(CH2)s-, (CH2)r-O(CH2)s-O, (CH2)r-CO, (CH2)r-COO, (CH2)r-OCO, (CH2)r-NR2-, (CH2)r-CONR2-, (CH2)r-NR2-CO, (CH2)r-NR2-COO or (CH2)r-NR2-CONR3-, wherein the suffix r is a whole number between 4 and 24, preferably between 5 and 12, more preferably between 5 and 10, even more preferably between 5 and 8, especially between 6 and 8 and and R.sup.2 and R.sup.3 each independently signify hydrogen or lower alkyl;

7. The photoaligning polymer material according to claim 1, wherein D is a 2,2,2-trifluoro-ethyl group.

8. The photoaligning polymer material according to claim 1, wherein M.sup.1 and M.sup.1 are methacrylate.

9. A composition comprising a photoaligning polymer material according to claim 1, at least a solvent and at least an additive.

10. The composition according to claim 9 wherein the additive is selected from the group consisting of polymerizable liquid crystal, UV curable compounds, crosslinking agents, silane-containing compounds, photo-active additives, photo-initiators, surfactats, emulsifiers, antioxidant, levelling agent, dyes, epoxy-containing crosslinking agents and curable compounds.

11. A method comprising: using the photoaligning polymer materials according to claim 1 as orienting layer for liquid crystals.

12. A method for the preparation of an orientation layer for liquid crystals comprising: irradiating photoaligning polymer material according to claim 1 with aligning light.

13. Orientation layers obtained by the method according to claim 12.

14. Orientation layers comprising a photoaligning polymer material according to claim 1.

15. Optical, electro-optical or nanoelectrical elements comprising photoaligning polymer material according to claim 1.

16. A method comprising: using the composition according to claim 9 as orienting layer for liquid crystals.

17. A method for the preparation of an orientation layer for liquid crystals comprising: irradiating the composition according to claim 9 with aligning light.

18. Orientation layers comprising a composition according to claim 9.

19. Optical, electro-optical or nanoelectrical elements comprising a composition according to claim 9.

20. Optical, electro-optical or nanoelectrical elements comprising an orientation layer according to claim 13.

Description

EXAMPLES

Example 1

[0264] Synthesis of Compound 1.

Preparation of 6-[4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenoxy]hexyl 2-methylprop-2-enoate

[0265] ##STR00010##

[0266] 400.1 g of 4-hydroxybenzaldehyde, 588.4 g of potassium carbonate (powder), 40.0 g of potassium iodide and 0.4 g of phenothiazine are suspended in 1600 g of DMF. To this suspension 710.7 g of 6-chlorohexyl 2-methylprop-2-enoate are added. The resulting mixture is then heated up to 85 C. under nitrogen atmosphere. After 18 hours at 85 C. the reaction mixture is cooled down to 20 C. and filtered over Hyflo. The remaining solid is washed with 400 g of DMF. The resulting DMF solution is transferred in a reactor. To this solution 0.6 g of phenothiazine, 0.6 g pf BHT, 727.98 g of propanedioic acid, 1-(2,2,2-trifluoroethyl) ester in 250 g of DMF and 114 g of morpholine are added. The reaction mixture is then stirred under nitrogen at 50 C. After 6 hours the reaction is cooled down to RT, and then isopropanol is added. Water is then added dropwise to precipitate the product out of the orange solution. After filtration and washing 1080 g of Compound 2 are obtained as a white solid with an HPLC purity of >97%.

[0267] 1H NMR (300 MHz) in CDCl3 of compound 2: 7.75 (d, 1H), 7.51 (d, 2H), 6.91 (d, 2H), 6.35 (d, 1H), 6.11 (m, 1H), 5.56 (m, 1H), 4.60 (dd, 2H), 4.18 (t, 2H), 4.02 (t, 2H), 1.96 (m, 3H), 1.84 (m, 2H), 1.74 (m, 2H), 1.51 (m, 4H).

Example 2

[0268] Synthesis of Compound 2.

Preparation of 6-[2-methoxy-4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenoxy]hexyl 2-methylprop-2-enoate

[0269] ##STR00011##

[0270] Similarly to the previous example, the condensation of 6-chlorohexyl 2-methylprop-2-enoate with vanillin, followed by the condensation with propanedioic acid, 1-(2,2,2-trifluoroethyl) ester lead to the synthesis of Compound 2 in 78% yield with an HPLC purity of >97%.

[0271] 1H NMR (300 MHz) in DMSO-d6 of Compound 3: 7.70 (d, 1H), 7.42 (d, 1H), 7.26 (d, 1H), 6.98 (d, 1H), 6.68 (d, 1H), 6.02 (m, 1H), 5.66 (m, 1H), 4.85 (dd, 2H), 4.10 (t, 2H), 4.03 (t, 2H), 3.81 (s, 3H), 1.88 (m, 3H), 1.72 (m, 2H), 1.64 (m, 2H), 1.43 (m, 4H).

Example 3

[0272] Synthesis Example of Compound 3.

Preparation of 8-[2-methoxy-4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenoxy]octyl 2-methylprop-2-enoate

[0273] ##STR00012##

[0274] Similarly to examples 1 and 2, the condensation of 8-chlorooctyl 2-methylprop-2-enoate with 4-hydroxybenzaldehyde, followed by the condensation with propanedioic acid, 1-(2,2,2-trifluoroethyl) ester resulted in the synthesis of Compound 3 in 70% yield with an HPLC purity of >97%.

[0275] 1H NMR (300 MHz) in CDCl3 of Compound 4: 7.73 (d, 1H), 7.47 (d, 2H), 6.91 (d, 2H), 6.35 (d, 1H), 6.09 (m, 1H), 5.56 (m, 1H), 4.57 (dd, 2H), 4.14 (t, 2H), 3.98 (t, 2H), 1.94 (m, 3H), 1.77 (m, 2H), 1.68 (m, 2H), 1.45 (m, 8H).

Example 4

[0276] Synthesis of Compound 4.

Preparation of 8-[2-methoxy-4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenoxy]octyl 2-methylprop-2-enoate

[0277] ##STR00013##

[0278] As described for Compound 2, the condensation of 8-chlorooctyl 2-methylprop-2-enoate with vanillin, followed by the condensation with propanedioic acid, 1-(2,2,2-trifluoroethyl) ester lead to Compound 4 in 60% yield with an HPLC purity of >95%.

[0279] 1H NMR (300 MHz) in DMSO-d6 of Compound 5: 7.70 (d, 1H), 7.42 (d, 1H), 7.30 (d, 1H), 7.00 (d, 1H), 6.70 (d, 1H), 6.01 (m, 1H), 5.66 (m, 1H), 4.85 (dd, 2H), 4.10 (t, 2H), 3.99 (t, 2H), 3.80 (s, 3H), 1.87 (m, 3H), 1.72 (m, 2H), 1.61 (m, 2H), 1.33 (m, 8H).

Example 5

[0280] Synthesis of Compound 5.

Preparation of [2-methoxy-4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenyl]4-(6-prop-2-enoyloxyhexoxy)benzoate

[0281] ##STR00014##

[0282] As described for Compound 2, the condensation of 8-chlorooctyl 2-methylprop-2-enoate with (4-formyl-2-methoxy-phenyl) 4-hydroxybenzoate, followed by the condensation with propanedioic acid, 1-(2,2,2-trifluoroethyl) ester lead to Compound 5 in 76% yield with an HPLC purity of >93%.

[0283] 1H NMR (300 MHz) in DMSO-d6 of Compound 6: 8.06 (d, 2H), 7.83 (d, 1H), 7.78 (s, 1H), 7.40 (d, 1H), 7.30 (d, 1H), 7.11 (d, 2H), 6.90 (d, 1H), 6.30 (d, 1H), 6.20 (dd, 1H), 5.95 (d, 1H), 4.90 (dd, 2H), 4.10 (m, 4H), 3.83 (s, 3H), 1.77 (m, 2H), 1.65 (m, 2H), 1.44 (m, 4H).

Example 6

Synthesis of Poly-6-[4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenoxy]hexyl 2-methylprop-2-enoate

[0284] ##STR00015##

[0285] 25 g of monomeric Compound 1 as synthesized in Example 1 are dissolved in cyclohexanone (CHN) under stirring in nitrogen atmosphere. The reaction mixture is then heated up to 75 C. and then 0.4 g of Luperox LP (Lauryl peroxide) are added. The reaction mixture is then maintained at 75 C. for 5 hours then the temperature is increased to 100 C. After 1 hour at 100 C. the reaction mixture is cooled down to RT and then filtered to obtain the polymer in CHN solution (Mw=151000 and Mn=41800). This photoaligning polymer material is named PAM1.

Example 7

Synthesis of a copolymer of 6-[4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenoxy]hexyl 2-methylprop-2-enoate and 6-[4-[(E)-3-methoxy-3-oxo-prop-1-enyl]phenoxyhexyl 2-methylprop-2-enoate

[0286] ##STR00016##

[0287] The copolymer is prepared according to the process described for Example 1 by using 14 g of Compound 1, 11 g of 6-[4-[(E)-3-methoxy-3-oxo-prop-1-enyl]phenoxyhexyl 2-methylprop-2-enoate in 100 g of CHN and 0.4 g of Luperox LP. The copolymer is obtained in CHN solution (Mw=123200 and Mn=39500). This photoaligning polymer material is named PAM2.

Example 8

[0288] Synthesis of Comparative Photoalignment Polymers

[0289] Photoaligning polymer material 3 (PAM3) has been synthesized as described in patent application WO2012/085048 A1.

##STR00017##

[0290] Photoaligning polymer material 4 (PAM4) has been synthesized as described in Example A4 in patent application WO2015/024810 A1.

##STR00018##

[0291] Photoaligning polymer material 5 (PAM5) has been synthesized as described in patent application JP 2005-326439 A.

##STR00019##

[0292] Photoaligning polymer material 6 (PAM6) has been synthesized in a similar way as described in example 2 of the patent application WO2012/085048 A1.

##STR00020##

Example 9

Synthesis of Poly-6-[2-methoxy-4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenoxy]hexyl 2-methylprop-2-enoate

[0293] ##STR00021##

[0294] According to the process described for Example 6, the polymer is obtained in CHN solution by using monomeric Compound 2 (Mw=160700 and Mn=59500). This photoaligning polymer material is named PAM7.

Example 10

Synthesis of Poly-8-[2-methoxy-4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenoxy]octyl 2-methylprop-2-enoate

[0295] ##STR00022##

[0296] According to the process described for Example 6, the polymer is obtained in CHN solution by using monomeric Compound 3 (Mw=131600 and Mn=53200). This photoaligning polymer material is named PAM8.

Example 11

Synthesis of Poly-8-[2-methoxy-4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenoxy]octyl 2-methylprop-2-enoate

[0297] ##STR00023##

[0298] According to the process described for Example 6, the polymer is obtained in CHN solution by using monomeric Compound 4 (Mw=212100 and Mn=66100). This photoaligning polymer material is named PAM9.

Example 12

Synthesis of Poly-[2-methoxy-4-[(E)-3-oxo-3-(2,2,2-trifluoroethoxy)prop-1-enyl]phenyl]4-(6-prop-2-enoyloxyhexoxy)benzoate

[0299] ##STR00024##

[0300] According to the process described for Example 6, the polymer is obtained in CHN solution by using monomeric Compound 5 (Mw=228000 and Mn=32900). This photoaligning polymer material is named PAM10.

Example 13

[0301] Preparation of Photoaligning Composition 1 (PAC1)

[0302] The solution PAC1 is prepared by adding 3 wt % of the photoalignment material PAM1 in 97 wt % of methoxypropylacetate and stirring the mixture for 30 minutes at room temperature.

Example 14

[0303] Preparation of Photoaligning Composition 2 (PAC2)

[0304] The solution PAC2 is prepared by adding 3 wt % of the photoalignment material PAM3 in 97 wt % of methoxypropylacetate and stirring the mixture for 30 minutes at room temperature.

Example 15

[0305] Preparation of Photoaligning Composition 3 (PAC3)

[0306] The solution PAC3 is prepared by adding 2 wt % of the photoalignment material PAM6 in 98 wt % of methoxypropylacetate and stirring the mixture for 30 minutes at room temperature.

Example 16

[0307] Preparation of Photoaligning Composition 4 (PAC4)

[0308] The solution PAC4 is prepared by adding 3 wt % of the photoalignment material PAM4 in 97 wt % of methoxypropylacetate and stirring the mixture for 30 minutes at room temperature.

Example 17

[0309] Preparation of Photoaligning Composition 5 (PAC5)

[0310] The solution PAC5 is prepared by adding 3 wt % of the photoalignment polymer PAM5 in 97 wt % of methoxypropylacetate and stirring the mixture for 30 minutes at room temperature.

Example 18

[0311] Preparation of Photoaligning Composition 6 (PAC6)

[0312] The solution PAC6 is prepared by adding 3 wt % of the photoalignment polymer PAM7 in 97 wt % of methoxypropylacetate and stirring the mixture for 30 minutes at room temperature.

Example 19

[0313] Preparation of Photoaligning Composition 7 (PAC7)

[0314] The solution PAC7 is prepared by adding 3 wt % of the photoalignment polymer PAM8 in 97 wt % of methoxypropylacetate and stirring the mixture for 30 minutes at room temperature.

Example 20

[0315] Preparation of Photoaligning Composition 8 (PAC8)

[0316] The solution PAC8 is prepared by adding 3 wt % of the photoalignment polymer PAM9 in 97 wt % of methoxypropylacetate and stirring the mixture for 30 minutes at room temperature.

Example 21

[0317] Preparation of Photoaligning Composition 9 (PAC9)

[0318] The solution PAC9 is prepared by adding 3 wt % of the photoalignment polymer PAM10 in 97 wt % of methoxypropylacetate and stirring the mixture for 30 minutes at room temperature.

Examples 22-33

[0319] Preparation of Photo-Orientable Materials.

[0320] Following curable compositions were prepared:

[0321] Curable Composition 1 (CC1) is prepared by mixing 20 wt % of:

TABLE-US-00001 55.95% Laromer 9050 (BASF) 37.90% 1,6-Hexanediol-diacrylate (Sigma Aldrich) 5.05% Irgacure 907 (BASF) 1.00% Tinuvin 144 (BASF) 0.10% BHT (Sigma Aldrich)
in n-Butylacetate (BA) and stirring 30 minutes at RT.

[0322] The Curable Composition 2 (CC2) was prepared by mixing 20 wt % of OC-4021 (DYMAX) in n-Butylacetate (BA) and stirring 30 minutes at RT.

Example 22

[0323] Preparation of Photo-Orientable Material 1 (POM1)

[0324] The photo-orienting solution POM1 is prepared by mixing 1 wt % of the photoalignment material PAM1 in CC1 and stirring the mixture for 30 minutes at room temperature.

Example 23

[0325] Preparation of Photo-Orientable Material 2 (POM2)

[0326] The photo-orienting solution POM2 is prepared by mixing 1 wt % of the photoalignment material PAM5 in CC1 and stirring the mixture for 30 minutes at room temperature.

Example 24

[0327] Preparation of Photo-Orientable Material 3 (POM3)

[0328] The photo-orienting solution POM3 is prepared by mixing 1 wt % of the photoalignment material PAM4 in CC1 and stirring the mixture for 30 minutes at room temperature.

Example 25

[0329] Preparation of Photo-Orientable Material 4 (POM4)

[0330] The photo-orienting solution POM4 is prepared by mixing 1 wt % of the photoalignment material PAM2 in CC1 and stirring the mixture for 30 minutes at room temperature.

Example 26

[0331] Preparation of Photo-Orientable Material 5 (POM5)

[0332] The photo-orienting solution POM5 is prepared by mixing 1 wt % of the photoalignment material PAM1 in CC2 and stirring the mixture for 30 minutes at room temperature.

Example 27

[0333] Preparation of Photo-Orientable Material 6 (POM6)

[0334] The photo-orienting solution POM6 is prepared by mixing 1 wt % of the photoalignment material PAM4 in CC2 and stirring the mixture for 30 minutes at room temperature.

Example 28

[0335] Preparation of Photo-Orientable Material 7 (POM7)

[0336] The photo-orienting solution POM7 is prepared by mixing 1 wt % of the photoalignment material PAM8 in CC2 and stirring the mixture for 30 minutes at room temperature.

Example 29

[0337] Preparation of Photo-Orientable Material 8 (POM8)

[0338] The photo-orienting solution POM7 is prepared by mixing 1 wt % of the photoalignment material PAM7 in CC2 and stirring the mixture for 30 minutes at room temperature.

Example 30

[0339] Preparation of Photo-Orientable Material 9 (POM9)

[0340] The photo-orienting solution POM7 is prepared by mixing 2 wt % of the photoalignment material PAM7 in CC2 and stirring the mixture for 30 minutes at room temperature.

Example 31

[0341] Preparation of Photo-Orientable Material 10 (POM10)

[0342] The photo-orienting solution POM7 is prepared by mixing 1 wt % of the photoalignment material PAM9 in CC2 and stirring the mixture for 30 minutes at room temperature.

Example 32

[0343] Preparation of Photo-Orientable Material 11 (POM11)

[0344] The photo-orienting solution POM7 is prepared by mixing 2 wt % of the photoalignment material PAM9 in CC2 and stirring the mixture for 30 minutes at room temperature.

Example 33

[0345] Preparation of Photo-Orientable Material 12 (POM12)

[0346] The photo-orienting solution POM7 is prepared by mixing 1 wt % of the photoalignment material PAM10 in CC2 and stirring the mixture for 30 minutes at room temperature.

Examples 34-40

[0347] Preparation of the compositions comprising the Polymerizable Liquid Crystal and the Photo Orientable Material (PLCPO-M1-PCLPO-M7).

[0348] All compositions comprise:

TABLE-US-00002 97.775% LCC2 1.000% Irgacure 907 (BASF) 0.200% Tinuvin 123 (BASF) 0.025% BHT (Sigma Aldrich) 1.000% PAM

[0349] LCC2:

[0350] O5-[4-[3-methyl-4-[4-[5-oxo-5-(2-prop-2-enoyloxyethoxy)pentanoyl]oxybenzoyl]oxy-phenoxy]carbonylphenyl]O1-(2-prop-2-enoyloxyethyl) pentanedioate

##STR00025##

Example 34

[0351] PLCPO-M1 contains 1% of PAM1.

Example 35

[0352] PLCPO-M2 contains 1% of PAM4.

Example 36

[0353] PLCPO-M3 contains 1% of PAM5.

Example 37

[0354] PLCPO-M4 contains 1% of PAM8.

Example 38

[0355] PLCPO-M5 contains 1% of PAM7.

Example 39

[0356] PLCPO-M6 contains 1% of PAM9.

Example 40

[0357] PLCPO-M7 contains 1% of PAM10.

[0358] The different PLCPO-Ms were dissolved in a solvent mixture of 20% Butylacetate and 80% cyclohexanone and stirred the mixture for 30 minutes at room temperature in a 35:65 ratio.

APPLICATION EXAMPLES

Example 41

[0359] Preparation of a Primer Coated Substrate

[0360] A triacetate cellulose (TAC) foil was coated by means of Kbar coater (bar size 1) with a primer solution (DYMAX OC-4021). The film was dried at 80 C. for 30 s and the thickness of the resulting film was about 2 m. Then the film was exposed to UV light (1500 mJ, under nitrogen atmosphere).

Example 42

[0361] Preparation of an Orientation Layer Using Photoalignment Materials

[0362] A primer coated TAC substrate of Application Example 1 was Kbar coated (bar size 0) with a Photoalignment Composition (PAC). The film was dried at 80 C. for 30 s and the resulting film thickness was about 100 nm. Then the film was exposed to aligning light, which was collimated and linearly polarized UV (LPUV) light (280-320 nm) with various exposure energy from 10 to 100 mJ/cm.sup.2. The plane of polarization was 0 with regard to a reference edge on the TAC substrate.

Example 43

[0363] Preparation of an Orientation Layer Using Photo Orientable Materials

[0364] A triacetate cellulose (TAC) foil was coated by means of Kbar coater (bar size 0) with a POM solution. The film was dried at 80 C. for 60 s; the thickness of the resulting film was about 2 m. Then the film was exposed to UV light (500 mJ under nitrogen atmosphere for curable composition CC1 and 1500 mJ under nitrogen atmosphere for curable composition CC2). The film was then exposed to aligning light, which was collimated and linearly polarized UV (LPUV) light (280-320 nm) with various exposure energy from 10 to 100 mJ/cm.sup.2. The plane of polarization was 0 with regard to a reference edge on the TAC substrate.

Example 44

[0365] Preparation of an Orientation Layer Using Polymerizable Liquid Crystal and Photo Orientable Material

[0366] An orientation layer as of Application Example 2 was prepared with a plane of polarization of 20 with regard to a reference edge of the primer coated substrate (Application Example 1). This layer was Kbar coated (bar size 2) with a PLCPO-M solution (produced as described above). The layer was dried at 50 C. for 60 s and subsequently the liquid crystals were cross-linked at room temperature under nitrogen atmosphere by UV-A light exposure 200 mJ/cm.sup.2. The PLCPO-M layer was then exposed to collimated LPUV light (280-320 nm) with various exposure energy from 10 to 100 mJ/cm2. The plane of polarization was 80 with regard to a reference edge on the TAC substrate.

Example 45

[0367] Preparation of an LCP Layer Aligned by the Orientation Layer

[0368] An LCP layer is prepared on top of the orientation layer of examples 42, 43 or 44 by Kbar coating (bar size 1) the LCP solution S-LCC1. The wet layer was dried at 50 C. for 60 s and subsequently the liquid crystals are cross-linked at room temperature under nitrogen atmosphere by UV-A light exposure of 30 mW/cm.sub.2 for 50 seconds.

[0369] Following crosslinkable liquid crystal compound (LCC) was used: LCC1:

pentyl 2,5-bis[[4-(6-prop-2-enoyloxyhexoxy)benzoyl]oxy]benzoate

[0370] ##STR00026##

[0371] The solution S-LCC1 is prepared by dissolving 35 wt % of

TABLE-US-00003 98.525% LCC1 1.00% Irgacure 907 (BASF) 0.20% Tinuvin 123 (BASF) 0.25 Tegoflow 300 (Evonik) 0.025% BHT (Sigma Aldrich)
in 65 wt % of a solvent mixture of 80% n-butylacetate and 20% Cyclohexanone and stirring the mixture for 30 minutes at room temperature.

[0372] Examples 46-48

[0373] Evaluation of the Quality of Orientation

[0374] For an efficient manufacturing process it is of interest to know how much exposure energy does a photo-alignment layer require to achieve a good visible and homogeneous (without any visible defect) contrast in a LCP layer aligned by the orientation layer. The films produced have been analysed between crossed polarizers. Alignment quality has been ranked as the following: [0375] .box-tangle-solidup..box-tangle-solidup. very good alignment homogeneous orientation [0376] .box-tangle-solidup. good orientation (disclination lines (DL's) area <2% of coating area) [0377] few DL's (<10% of coating area) [0378] DL's visible (>10% of coating area) [0379] inhomogeneous orientation or no orientation

Example 46

[0380] Optical devices have been produced by the following sequence: a primer coated substrate (as produced in Application Example 41) has been coated by an orientation layer using PAM materials (as described in Application Example 42) and orienting an LCP layer (as shown in Application Example 45). Various exposure energies have been used to orient the PAM materials. Summary of the results are shown in the Table 1 below. The results show that the compounds according to the present invention orient the liquid crystals at lower energy compared e.g. to the compound according to the prior art.

TABLE-US-00004 TABLE 1 LPUV dosage (mJ/cm.sup.2) 10 20 30 40 50 60 70 80 90 100 150 200 250 PAM1 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. PAM4 PAM5 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. PAM7 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. PAM8 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. PAM9 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. PAM10 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup.

Example 47

[0381] Optical devices have been produced by the following sequence: an orientation layer was prepared as described in Example 43 using POM materials, followed by coating and orienting an LCP layer (as shown in Example 45). Various exposure energies have been used to orient the POM materials. Summary of the results are shown in the Table 2 below. The results show that the compounds according to the present invention orient the liquid crystals at lower energy compared e.g. to the compound according to the prior art. Further the results demonstrate that the compounds (homopolymers or copolymers) according to the present invention are suited for the orientation in different curable compositions

TABLE-US-00005 TABLE 2 LPUV dosage (mJ/cm.sup.2) 10 20 25 40 50 60 70 80 90 100 150 200 POM1 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. POM3 .box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. POM4 .box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. POM5 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. POM6 .box-tangle-solidup. .box-tangle-solidup. .box-tangle-solidup. .box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. POM7 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup.

Example 48

[0382] Optical devices have been produced by the following sequence: a primer coated substrate (as produced in Example 41) has been coated by an orientation layer using PAM2 material (as described in Example 42 and with 100 mJ/cm.sup.2 as LPUV dosage) an orientation layer using PLCPO materials was prepared as described in Example 44, followed by the coating and orienting an LCP layer (as shown in Example 45). Various exposure energies have been used to orient the PLCPO layer. Summary of the results are shown in the Table 3 below. The results show that the compounds according to the present invention achieve a better orientation compared to the compounds of the prior art.

TABLE-US-00006 TABLE 3 LPUV dosage (mJ/cm2) 10 20 30 40 50 60 70 80 90 100 150 200 250 PLCPO-M1 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. PLCPO-M2 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. PLCPO-M3 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. PLCPO-M4 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. PLCPO-M7 .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup. .box-tangle-solidup..box-tangle-solidup.

Example 49

[0383] A liquid crystal cell is prepared wherein the liquid crystal is aligned by photoalignment material PAM1 and the electric field is applied between two plan electrodes on each side of the cell gap.

[0384] A 6 wt % solution is prepared by mixing the photoalignment material PAM in CHN (cyclohexanone). The above polymer solution was spin-coated onto the two ITO coated glass substrates at a spin speed of 1000 rpm for 30 seconds. After spin coating the substrates are subjected to baking at a temperature of 100 C. for 4 minutes. The resulting layer thickness is around 300 nm. The substrates with the coated polymer layer on top are exposed to linearly polarized UV light (LPUV) at an incidence angle of 60 relative to the normal of the substrate surface. The plane of polarization was within the plane spanned by the substrate normal and the propagation direction of the light. The applied exposure dose is 200 mJ/cm.sup.2 or 250 mJ/cm.sup.2. After LPUV exposure, a cell is assembled with the 2 substrates, the exposed polymer layers facing to the inside of the cell. The substrates are adjusted relative to each other such that the induced alignment directions are anti-parallel to each other. The cell is capillary filled with liquid crystal MLC7067 (Merck KGA), which had a positive dielectric anisotropy. After that, the cell is annealed at 100 C. for 30 minutes and cooled down to room temperature. Alignment quality of the liquid crystal in the cell is checked by placing the cell between two crossed polarizers and adjusted to obtain dark state. The alignment quality is defined to be good (rating 5), if the dark state show no defects and the liquid crystal is well oriented. The alignment quality is defined to be medium (rating 3) if the dark state has light leakage because of slight inhomogeneous orientation of liquid crystal in some areas of the cell. The alignment quality is defined to be worse (rating 0), if liquid crystal is not oriented with absence of dark state.

[0385] Cells are prepared with PAM1, PAM7, PAM8, PAM9 and PAM10 according to the process described above. The liquid crystal in all cells showed well defined and homogeneous planar orientation after thermal annealing of the cells. Pre-tilt angles of below 1 are measured using the rotating analyzer method from Shintech. The results are summarized in the Table 4 below.

TABLE-US-00007 TABLE 4 Photoalignment Cell gap LPUV dosage Alignment Pre-tilt Material (m) (mJ/cm.sup.2) Quality Angle () PAM1 12.44 200 5 0.46 PAM1 12.77 250 5 0.77 PAM6 12.78 200 3 0.31 PAM7 12.62 200 5 0.13 PAM7 12.62 250 5 0.13 PAM8 12.35 200 5 0.30 PAM8 12.80 250 5 0.73 PAM9 12.40 200 5 0.16 PAM9 12.59 250 5 0.21 PAM10 12.53 200 5 0.09 PAM10 12.94 250 4 0.04

[0386] The results show that all the compounds according to the present invention have a very good alignment quality compared to the compound of the prior art.

Example 50

[0387] Adhesion Test

[0388] A PET-ITO substrate is removed from its protective liner. The surface is activated by means of a Coronna treatment (300 W, 120 m/min 6). Right after the activation step, the alignment material is coated onto the substrate by spin-coating (1000 rpm for 30 s) and a 300 nm thick layer is obtained.

[0389] The sample is baked at 100 C. for 4 min and exposed to LPUV at an incidence angle of 50 relative to the normal of the substrate surface. The applied exposure dose is 200 and 250mJ/cm2.

[0390] The adhesion is measured according the cross-test cut described in DIN EN ISO 2409.

[0391] The used tape is from Nichiban.

[0392] The results are summarized in the Table 5 below:

TABLE-US-00008 TABLE 5 Photoalignment LPUV dosage Material (mJ/cm.sup.2) Adhesion PAM1 200 GT 1 PAM1 250 GT 1 PAM6 200 GT 4 PAM8 200 GT 1 PAM8 250 GT 1 PAM10 200 GT 1 PAM10 250 GT 2

[0393] The results show that all fluorinated compounds without have a better adhesion parameter compared to the prior art compound.